CN106348266B - The method that hemihydrate technique prepares phosphoric acid coproduction land plaster - Google Patents
The method that hemihydrate technique prepares phosphoric acid coproduction land plaster Download PDFInfo
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- CN106348266B CN106348266B CN201610717263.3A CN201610717263A CN106348266B CN 106348266 B CN106348266 B CN 106348266B CN 201610717263 A CN201610717263 A CN 201610717263A CN 106348266 B CN106348266 B CN 106348266B
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- phosphoric acid
- hemihydrate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
- C01B25/223—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen only one form of calcium sulfate being formed
- C01B25/226—Hemihydrate process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention belongs to phosphorous chemical industry production technical fields, and in particular to a kind of method of producing phosphoric acid by hemihydrate technique and coproduction land plaster.Aiming at the problem that existing hemihydrate technique coproduction gypsum is unsatisfactory for building gypsum standard, the present invention provides a kind of method of producing phosphoric acid by hemihydrate technique and coproduction land plaster.The method of the invention includes: that the slurry of crystallization tank returns to anterior reactor, with phosphorus ore pre-reaction；Remaining SO in reactive tank, in overfall4 2‑It is further sufficiently reacted with the CaO in phosphorus ore；H is added in crystallization tank2SO4, semi-hydrated gypsum is obtained, is filtered, washed, de- free water, obtains the land plaster of 2~10 ﹕ 1 of draw ratio.Building gypsum standard requirements are better than using the setting time of the land plaster of technique preparation, flexural strength, compression strength.The gypsum subsequent processing difficulty that phosphoric acid is prepared with energy saving, shortening process, solution hemihydrate technique, widens the utilization scope of ardealite, reduces gypsum stockyard and stores up pressure.
Description
Technical field
The invention belongs to phosphorous chemical industry production technical fields, and in particular to a kind of hemihydrate technique prepares phosphoric acid coproduction land plaster
Method.
Background technique
During Wet-process Phosphoric Acid Production, with process conditions such as reaction process slurry temperature, phosphoric acid concentration, sulfuric acid dosages
Difference, CaSO4Hydrate there are three types of different shape exist, i.e. two water objects, half water object and anhydride.According to generation CaSO4Crystallization
The difference of form, Wet-process Phosphoric Acid Production process mainly have dihydrate process, hemihydrate process, Ban Shui-dihydrate process and two water-
Hemihydrate process.Overwhelming majority phosphoric acid production is using dihydrate process at present, but because having, low energy consumption, section for hemihydrate process
About sulfuric acid, obtained phosphoric acid concentration height, coproduction have many advantages, such as the semi-hydrated gypsum of gelling, just gradually develop into phosphoric acid by wet process
Main flow.
Ardealite is the solid waste of Wet-process Phosphoric Acid Production process discharge, produces 1t phosphoric acid (with P2O5Meter) phosphorus need to be discharged
Gypsum 5.5t.The stacking of ardealite does not only take up a large amount of land resource, and gypsum cinder field construction cost is expensive, the infiltration of gypsum cinder field
Water easily causes underground water pollution, and there are larger security risks.The comprehensive utilization and harmless treatment of ardealite will become phosphatization
The bottleneck of work Business survival and development is the vital task that current phosphorous chemical industry enterprise faces.
Patent CN1844009A describes the method for preparing building gypsum with ardealite, handles first with carbonate mountain flour
Free P and free F in ardealite, then constant temperature is handled in 150~210 DEG C of calciners, is dried and is lost free water and partially tie
Brilliant water, obtains building gypsum.
Patent CN102731000A describes a kind of method using half water and phosphogypsum dihydrate production building gypsum, allotment
Dihydrate gypsum and semi-hydrated gypsum ratio, 140~200 DEG C of calcinings, when can reduce energy consumption, control the initial set and final set of building gypsum
Between.
The common ground of the above ardealite processing method are as follows: at the solid waste of Wet-process Phosphoric Acid Production process discharge
Reason, process is complicated, energy consumption is high, and gypsum quality is unstable.Energy consumption and quality problem, patent are handled to solve ardealite
CN103086335A produces P using-half water Wet Processes of Phosphoric Acid of two water2O5- half water stone of phosphoric acid coproducing alpha of concentration 35%~39%
Cream, as building gypsum or as ardealite phosphoric acid co-producing cement raw material.But the invention obtains alpha-semi water plaster stone initial set, final set
Time, early strength are difficult to meet the requirement of building gypsum, and preparation process flow is long, high production cost.
Summary of the invention
The technical problem to be solved by the present invention is to the presetting periods of the semi-hydrated gypsum of prior art production phosphoric acid coproduction, final set
Not the problem of time, the anti-folding of 2h and compression strength index are not able to satisfy building gypsum standard.
The present invention solves the technical solution of the technical problem are as follows: provides a kind of hemihydrate technique and prepares phosphoric acid coproduction land plaster
Method, the semi-hydrated gypsum crystallization of this method preparation is coarse, draw ratio is suitable, is able to satisfy the standard of building gypsum.
The present invention provides a kind of method that hemihydrate technique prepares phosphoric acid coproduction land plaster, comprising the following steps:
A, in anterior reactor, the slurry and phosphorus ore crystallized containing phosphoric acid, sulfuric acid and semi-hydrated gypsum is added, is carried out after mixing anti-
It answers；
B, product in anterior reactor is transferred in reactive tank, further sufficiently reaction；
C, product obtained in step b is transferred in crystallization tank, sulfuric acid is added, the reaction was continued obtains slurry；
D, by slurry filtration, washing in step c, phosphoric acid, cleaning solution and semi-hydrated gypsum crystallization is obtained, semi-hydrated gypsum knot is dried
Crystalline substance obtains land plaster.
Wherein, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, and slurry described in step a is mixed with phosphorus ore
Afterwards, the SO in solution4 2-Molar ratio with CaO is 0.3~0.8 ﹕ 1.
Wherein, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, and slurry liquid-solid ratio described in step a is
5~20 ﹕ 1.
Wherein, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, the additional amount of sulfuric acid in step c are as follows: make
The SO of slurry in step c crystallization tank4 2-Constant with CaO molar ratio is 1~5 ﹕ 1.
Wherein, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, and the slurry being added in step a is step c
Slurry made from middle reaction.
Wherein, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, and step c returns to the slurry in step a
Be added in weight and step a, c phosphorus ore sulfuric acid weight and ratio be 30~50 ﹕ 1.
Wherein, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, finished product phosphoric acid obtained in step d and is washed
It washs and is mixed in liquid return step c with sulfuric acid, back amount are as follows: guarantee that liquid-solid ratio is 5~20 ﹕ 1 in step c.
Wherein, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, elder generation and step before sulfuric acid is added in step c
The finished product phosphoric acid and cleaning solution returned in d is uniformly mixed.
Wherein, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, each reaction time described in step a~c
> 2h, total reaction time > 6h respectively.
Wherein, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, and reaction temperature described in step a~c is
93~98 DEG C.
The present invention also provides a kind of land plasters that the above method is prepared, and semi-hydrated gypsum before baking crystallizes major diameter
Than for 2~10 ﹕ 1.
The invention has the benefit that the present invention provides a kind of method of producing phosphoric acid by hemihydrate technique coproduction land plaster,
By controlling the liquid-solid ratio of producing phosphoric acid by hemihydrate technique process, returning the reaction of crystallization tank slurry return anterior reactor, control in slurry
SO4 2-Content meets the negative sulfuric acid condition of pre-reaction process, and the part phosphoric acid and cleaning solution that reaction is obtained return to crystallization
Slot increases liquid-solid ratio, reduces phosphoric acid, reduces the degree of supersaturation of extraction process, reduces extraction process nucleus production quantity, makes half
Water gypsum crystallization is grown up on existing crystal, improves semi-hydrated gypsum crystal habit.Micro- sem observation discovery: the half of spherical druse
Water gypsum crystallization is changed into the semi-hydrated gypsum crystallization of strip druse；Modified gypsum is seen after supersonic oscillations with electron microscope
Discovery is examined, 2~10 ﹕ 1 of draw ratio of strip crystallization.
Presetting period, final setting time and the intensity that the semi-hydrated gypsum that low energy consumption for this method, process is short, is prepared crystallizes are equal
It is able to satisfy the requirement of building gypsum plaster, and performance indicator is stablized, and can be used for making building gypsum, extends land plaster and use field,
Gypsum is widened using field, ardealite is turned waste into wealth, effectively administers pollution and harm of the ardealite to environment, therefore, half water
The method that technique produces phosphoric acid coproduction land plaster has good environmental benefit, Social benefit and economic benefit.
Specific embodiment
The present invention provides a kind of methods that hemihydrate technique prepares phosphoric acid coproduction land plaster, comprising the following steps:
A, in anterior reactor, the slurry and phosphorus ore crystallized containing phosphoric acid, sulfuric acid and semi-hydrated gypsum, slurry and phosphorus ore is added
Additional amount to meet the SO after the mixing of slurry phosphorus ore in solution4 2-Molar ratio with CaO is 0.3~0.8 ﹕ 1, slurry liquid-solid ratio
Subject to 5~20 ﹕ 1, reacted；
B, the product in anterior reactor is transferred in reactive tank, further sufficiently reaction；
C, the product in reactive tank is transferred in crystallization tank, sulfuric acid is added, the reaction was continued obtains slurry；The additional amount of sulfuric acid
Are as follows: guarantee SO in the slurry of crystallization tank4 2-Constant with CaO molar ratio is 1~5 ﹕ 1；
D, by slurry filtration, washing in step c, phosphoric acid, cleaning solution and semi-hydrated gypsum crystallization is obtained, semi-hydrated gypsum knot is dried
Crystalline substance obtains land plaster.
The present invention is reacted using anterior reactor, reactive tank and crystallization tank, and each reactive tank has respectively different effects.In advance
It returns to the free sulphur acid group in slurry using crystallization tank in reactive tank to react with phosphorus ore, mole of mixed sulfate radical and CaO
Than control in 0.3~0.8 ﹕ 1, the part CaO precipitating in phosphorus ore is generated into CaSO4.1/2H2O；When extending reaction in reactive tank
Between, it reacts the sulfate radical in overfall sufficiently with phosphorus ore, may advantageously facilitate the generation of CaSO4.1/2H2O and on having crystallization
Growth；After anterior reactor, reactive tank, containing the phosphorus ore not reacted completely in slurry, it is transferred to crystallization tank, adds sulfuric acid,
Phosphorus ore resolution ratio is improved, crystal form is further improved；Guarantee gypsum strainability, the unreacted sulfate radical in overfall continues
Participate in phosphorus ore pre-reaction.
If completing pre-reaction, reaction and crystalline growth in a reactive tank, hemihydrate technique is not met to crystalline growth ring
The requirement in border cannot obtain the semihydrate crystal of good crystalline, the sad filter of slurry, obtained gypsum crystallization poor crystal form, it is difficult to which satisfaction is built
Requirement of the material gypsum to initial set, final set and intensity.
The slurry main component being added in step a of the present invention is the semi-hydrated gypsum and P of certain liquid-solid ratio2O5Concentration be 40~
The mixture of 45% phosphoric acid, also containing free SO in slurry4 2-, the purpose of pre-reaction is to utilize the free SO in slurry4 2-With
Calcareous material reaction in phosphorus ore, makes SO present in the CaO and slurry in phosphorus ore4 2-Reaction generates semi-hydrated gypsum, due to material
Itself also containing semi-hydrated gypsum in slurry, new gypsum is just attached to the surface of original gypsum, newly-generated gypsum crystal form is changed,
The reaction for passing through step b, c again, the semi-hydrated gypsum crystallization 2~10:1 of draw ratio made, meets the requirement of building gypsum.
Wherein, the slurry being added in step a can be the slurry obtained of reaction in step c.Crystal form is better in order to obtain
Semi-hydrated gypsum, needs rate-determining steps c back to the slurry weight in step a, and phosphorus is added when returning in slurry weight and step a, b
Mine, sulfuric acid weight sum ratio be 30~50 ﹕ 1, obtained semi-hydrated gypsum crystal form is best.
The present invention provides advantage for gypsum crystallization, is to prepare to meet building gypsum mark by improving slurry liquid-solid ratio
The prerequisite of alignment request land plaster, but as the increase of liquid-solid ratio, device capability production capacity reduce, energy consumption is high, therefore, is
It obtains saving production cost while meeting the gypsum of building gypsum standard, the liquid-solid ratio of step a~c of the present invention is 5~20 ﹕
1。
In order to reduce saturation degree and phosphoric acid, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, step d
Obtained in finished product phosphoric acid and cleaning solution return step c, back amount are as follows: guarantee that liquid-solid ratio is 5~20 ﹕ 1 in step c, is returned
When be uniformly mixed in acid mixing device with sulfuric acid, add in crystallization tank.
It is carried out sufficiently to react, above-mentioned hemihydrate technique is prepared in the method for phosphoric acid coproduction land plaster, institute in step a~c
State each reaction time difference > 2h, total reaction time > 6h；Reaction temperature described in step a~c is 93~98 DEG C.
The present invention also provides a kind of land plasters that the above method is prepared, and semi-hydrated gypsum before baking crystallizes major diameter
Than for 2~10 ﹕ 1.
Presetting period, final setting time and the intensity for the alpha-semi water plaster stone that half water phosphoric acid process obtains in the prior art cannot expire
Sufficient building materials gypsum standard, mainly related with the crystallization shape of semi-hydrated gypsum, the present invention is to improve semi-hydrated gypsum crystallization, solid to liquid
Than, the parameters such as overfall amount, feed ratio are adjusted, be semi-hydrated gypsum by reducing the saturation degree and phosphoric acid of reaction process
Growth provides advantage, crystallizes newly-generated semi-hydrated gypsum and grows up on existing nucleus, to obtain coarse α-half water
Gypsum has remarkable result to improving gypsum setting time and improving building gypsum intensity.
Explanation is further explained to technical solution of the present invention below by embodiment, but therefore will be not of the invention
Protection scope is limited in range described in embodiment.
Each raw material of the present invention comes to ordinary commercial products, half water experimental provision by anterior reactor, reactive tank and
Crystallization tank is constituted, total dischargeable capacity 0.8m3。
Embodiment 1 prepares phosphoric acid coproduction land plaster with the method for the present invention
A, hemihydrate technique crystallization tank slurry is added in anterior reactor, slurry middle finger is designated as: P2O5: 42.05%, SO4 2-:
1.47%, CaO:0.15%, then into anterior reactor be added moisture content 12~13% phosphorus ore 12kg~12.5kg/h, guarantee
SO in liquid phase after slurry is mixed with phosphorus ore4 2-Molar ratio with CaO is 0.65 ﹕ 1, and reaction temperature is 93~98 DEG C, reaction 2~2.5
Hour；
B, the product in anterior reactor is transferred in reactive tank, makes residue SO in slurry4 2-With the CaO in phosphorus ore 93
~98 DEG C are further sufficiently reacted 2.5 hours；
C, product in reactive tank is transferred to crystallization tank, H is added in crystallization tank2SO4, formed and tied with calcium ion in liquid phase
Crystalline substance generates semi-hydrated gypsum, the amount of sulfuric acid is added with liquid phase SO in crystallization tank4 2-With CaO moles it is constant be subject to 3.15 ﹕ 1, at this time
Slurry liquid phase SO4 2-Content is 0.98%；It 93~98 DEG C, reacts 2.5 hours；
D, filtering for crystallizing slot slurry, and being washed using clear water, obtains product phosphoric acid, cleaning solution and semi-hydrated gypsum, and 80~85
DEG C dry lose free water, obtain coproduction land plaster.
In the present embodiment, the liquid-solid ratio of step a~d is 5 ﹕ 1, and part crystallization tank slurry returns to anterior reactor in step c,
The phosphorus ore being added and the ratio of sulfuric acid total weight are 38 ﹕ 1, cleaning solution and portioned product in step d in overfall amount and step a, c
Phosphoric acid mixes in return step c with sulfuric acid as acid reflux, and back amount is to guarantee that liquid-solid ratio is 5 ﹕ 1 in step c.Add in embodiment
Enter phosphorus ore 12.5kg/h, phosphoric acid yield 10.19kg/h, SO in finished product phosphoric acid4 2-It is reduced to 0.98%, phosphoric acid quality is unchanged.
Embodiment 2 prepares phosphoric acid coproduction land plaster with the method for the present invention
A, hemihydrate technique crystallization tank slurry is added in anterior reactor, slurry middle finger is designated as: P2O5: 42.05%, SO4 2-:
1.47%, CaO:0.15%, then into anterior reactor be added moisture content 12~13% phosphorus ore 12kg~12.5kg/h, guarantee
SO in liquid phase after slurry is mixed with phosphorus ore4 2-Molar ratio with CaO is 0.6 ﹕ 1, and reaction temperature is 93~98 DEG C, and reaction 2.5 is small
When；
B, the product in anterior reactor is transferred in reactive tank, makes residue SO in slurry4 2-With the CaO in phosphorus ore 93
~98 DEG C are further sufficiently reacted 2.5 hours；
C, product in reactive tank is transferred to crystallization tank, H is added in crystallization tank2SO4, formed and tied with calcium ion in liquid phase
Crystalline substance generates semi-hydrated gypsum, the amount of sulfuric acid is added with liquid phase SO in crystallization tank4 2-With CaO moles it is constant be to expect at this time subject to 2.1 ﹕ 1
Slurries phase SO4 2-Content is 0.66%；It 93~98 DEG C, reacts 2.5 hours；
D, filtering for crystallizing slot slurry, and being washed using clear water, obtains product phosphoric acid, cleaning solution and semi-hydrated gypsum, and 80~85
DEG C dry lose free water, obtain coproduction land plaster.
In the present embodiment, the liquid-solid ratio of step a~d is 10 ﹕ 1, and part crystallization tank slurry returns to pre-reaction in step c
The phosphorus ore being added and the ratio of sulfuric acid total weight are 35 ﹕ 1 in slot, overfall amount and step a, c, cleaning solution and part in step d
Product phosphoric acid mixes in return step c with sulfuric acid as acid reflux, and back amount is to guarantee that liquid-solid ratio is 10 ﹕ 1 in step c.Embodiment
Middle addition phosphorus ore 12kg/h, phosphoric acid yield 9.78kg/h, SO in finished product phosphoric acid4 2-It is reduced to 0.66%, phosphoric acid quality is unchanged.
Embodiment 3 prepares phosphoric acid coproduction land plaster with the method for the present invention
A, hemihydrate technique crystallization tank slurry is added in anterior reactor, slurry middle finger is designated as: P2O5: 42.05%, SO4 2-:
1.47%, CaO:0.15%, then into anterior reactor be added moisture content 12~13% phosphorus ore 12kg~12.5kg/h, guarantee
SO in liquid phase after slurry is mixed with phosphorus ore4 2-Molar ratio with CaO is 0.75 ﹕ 1, and reaction temperature is 93~98 DEG C, and reaction 2.5 is small
When；
B, the product in anterior reactor is transferred in reactive tank, makes residue SO in slurry4 2-With the CaO in phosphorus ore 93
~98 DEG C are further sufficiently reacted 2.5 hours；
C, product in reactive tank is transferred to crystallization tank, H is added in crystallization tank2SO4, formed and tied with calcium ion in liquid phase
Crystalline substance generates semi-hydrated gypsum, the amount of sulfuric acid is added with liquid phase SO in crystallization tank4 2-With CaO moles it is constant be subject to 1.32 ﹕ 1, at this time
Slurry liquid phase SO4 2-Content is 0.41%；It 93~98 DEG C, reacts 2.5 hours；
D, filtering for crystallizing slot slurry, and being washed using clear water, obtains product phosphoric acid, cleaning solution and semi-hydrated gypsum, and 80~85
DEG C dry lose free water, obtain coproduction land plaster.
In the present embodiment, the liquid-solid ratio of step a~d is 18 ﹕ 1, and part crystallization tank slurry returns to pre-reaction in step c
The phosphorus ore being added and the ratio of sulfuric acid total weight are 42 ﹕ 1 in slot, overfall amount and step a, c, cleaning solution and part in step d
Product phosphoric acid mixes in return step c with sulfuric acid as acid reflux, and back amount is to guarantee that liquid-solid ratio is 18 ﹕ 1 in step c.Embodiment
Middle addition phosphorus ore 12.2kg/h, phosphoric acid yield 9.94kg/h, SO in finished product phosphoric acid4 2-It is reduced to 0.41%.Phosphoric acid quality is without change
Change.
Comparative example 1 does not use the method for the present invention to prepare phosphoric acid coproduction land plaster
Slurry takes to semi-aquatic the crystallization tank for producing workshop, 2.5 ﹕ 1 of crystallization tank slurry liquid solid ratio when sampling；Crystallization tank slurry
Uninterrupted pumping is to anterior reactor, and overfall amount and the total weight ratio that feeds intake are 22 ﹕ 1, SO in liquid phase after guarantee slurry is mixed with phosphorus ore4 2-
Molar ratio with CaO is 0.7 ﹕ 1；H is added in crystallization tank2SO4, it is formed and is crystallized with calcium ion in liquid phase, generate semi-hydrated gypsum,
Liquid phase SO in crystallization tank4 2-With 6.5 ﹕ 1 of CaO molar ratio, crystallization tank is interior to extract slurry liquid phase SO4 2-Content is 2.05%.
In comparative example 1, pre-reaction, reaction and crystallization are in 2.5 ﹕ 1 of slurry liquid-solid ratio.The reduction of liquid-solid ratio, overfall amount reduce
Liquid phase SO to 22 ﹕ 1, in overfall4 2-It is increased to 2.05%.The extraction slurry degree of supersaturation of pre-reaction process, extraction slurry are viscous
Degree, the change of nucleus production quantity influence semi-hydrated gypsum crystalline environment, though obtained semi-hydrated gypsum is cluster crystal shape, crystallization is not grown
Greatly, P, F entrainment between crystal are big.The anti-folding of land plaster presetting period, final setting time and the 2h being obtained by extraction, compression strength are not inconsistent
Close building gypsum standard requirements.Phosphorus ore 12kg/h, phosphoric acid yield 9.58kg/h are added in comparative example, SO in finished product phosphoric acid4 2-:
2.05%.
Comparative example 2 does not use the method for the present invention to prepare phosphoric acid coproduction land plaster
Slurry takes to semi-aquatic the crystallization tank for producing workshop, 2.5 ﹕ 1 of crystallization tank slurry liquid solid ratio when sampling；Crystallization tank slurry
Uninterrupted pumping is to anterior reactor, and overfall amount and the total weight ratio that feeds intake are 37 ﹕ 1, SO in liquid phase after guarantee slurry is mixed with phosphorus ore4 2-
Molar ratio with CaO is 0.65 ﹕ 1；H is added in crystallization tank2SO4, it is formed and is crystallized with calcium ion in liquid phase, generate semi-hydrated gypsum,
Liquid phase SO in crystallization tank4 2-With 3.67 ﹕ 1 of CaO molar ratio, crystallization tank is interior to extract slurry liquid phase SO4 2-Content are as follows: 1.15%.
In comparative example 2, pre-reaction, reaction and crystallization are in 2.5 ﹕ 1 of slurry liquid-solid ratio.The reduction of liquid-solid ratio, 37 ﹕ 1 of overfall amount,
Liquid phase SO in overfall4 2-: 1.15%, liquid phase SO in pre-reaction process overfall4 2-It is with the molar ratio for putting into CaO in ground phosphate rock
0.65 ﹕ 1.Reduce the SO in overfall4 2-Slurry amount is returned in content, increase, alleviates the influence of double of water gypsum crystallization of degree of supersaturation, but
When liquid-solid ratio 2.5, the viscosity for extracting slurry is big, and it is poor that semi-hydrated gypsum growth is alleviated, though obtained semi-hydrated gypsum is cluster crystal shape, crystal
Between P, F entrainment it is big.The anti-folding of land plaster presetting period, final setting time and the 2h being obtained by extraction, compression strength do not meet building
Gypsum standard requirements.Phosphorus ore 12.3kg/h, phosphoric acid yield 9.82kg/h are added in comparative example, SO in finished product phosphoric acid4 2-: 1.15%.
Compliance test result
Performance measurement is carried out to the land plaster that embodiment and comparative example produces, measuring method is referring to GB/T9776-
2008 building gypsum plaster examination criterias, have obtained testing result shown in the following table 1.
Product index measured value obtained in 1 embodiment of table and comparative example
By embodiment and comparative example: in embodiment, being carried out by control liquid-solid ratio and overfall amount to gypsum crystallization
Improvement.Liquid phase SO in embodiment in overfall4 2-: 0.41%~0.98%, the liquid phase SO in comparative example overfall4 2-: 1.15%~
2.05%, reduced liquid phase sulfate radical content eliminates degree of supersaturation, reduces nucleus production quantity, controls semi-hydrated gypsum generating rate,
Finished product phosphoric acid SO4 2-It reduces, saves 4~36kg/ of sulfuric acid tons of P2O5；5~20 ﹕ 1 of liquid-solid ratio in embodiment, comparative example liquid-solid ratio are
2.5 ﹕ 1, the raising of liquid-solid ratio can reduce phosphoric acid, improve the generation and growth environment of semi-hydrated gypsum, half obtained water stone
Cream epigranular, draw ratio are 2~10 ﹕ 1,.Phosphoric acid coproduction land plaster is prepared with the method for the present invention, effectively solves land plaster initial set
Time, final setting time and the anti-folding of 2h, compression strength do not meet the technical problem of building gypsum standard requirements, and coproduction meets GB/
The land plaster of 3.0 standard of T9776-2008 building gypsum.
Claims (18)
1. the method that hemihydrate technique prepares phosphoric acid coproduction land plaster, which comprises the following steps:
A, in anterior reactor, the slurry and phosphorus ore crystallized containing phosphoric acid, sulfuric acid and semi-hydrated gypsum is added, is reacted after mixing；
SO after the slurry is mixed with phosphorus ore, in solution4 2-Molar ratio with CaO is 0.3~0.8 ﹕ 1；The liquid-solid ratio of the slurry
For 5~20 ﹕ 1；
B, product in anterior reactor is transferred in reactive tank, further sufficiently reaction；
C, product obtained in step b is transferred in crystallization tank, sulfuric acid is added, the reaction was continued obtains slurry；
D, by slurry filtration, washing in step c, phosphoric acid, cleaning solution and semi-hydrated gypsum crystallization are obtained, drying semi-hydrated gypsum crystallizes,
Obtain land plaster.
2. the method that hemihydrate technique according to claim 1 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step c
The additional amount of sulfuric acid are as follows: make the SO of slurry in step c crystallization tank4 2-Constant with CaO molar ratio is 1~5 ﹕ 1.
3. the method that hemihydrate technique according to claim 1 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step a
The slurry of addition is that slurry obtained is reacted in step c.
4. the method that hemihydrate technique according to claim 2 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step a
The slurry of addition is that slurry obtained is reacted in step c.
5. the method that hemihydrate technique according to claim 1 prepares phosphoric acid coproduction land plaster, it is characterised in that: step c is returned
Return in the slurry weight in step a and step a, c be added phosphorus ore sulfuric acid weight and ratio be 30~50 ﹕ 1.
6. the method that hemihydrate technique according to claim 2 prepares phosphoric acid coproduction land plaster, it is characterised in that: step c is returned
Return in the slurry weight in step a and step a, c be added phosphorus ore sulfuric acid weight and ratio be 30~50 ﹕ 1.
7. the method that hemihydrate technique according to claim 3 prepares phosphoric acid coproduction land plaster, it is characterised in that: step c is returned
Return in the slurry weight in step a and step a, c be added phosphorus ore sulfuric acid weight and ratio be 30~50 ﹕ 1.
8. the method that hemihydrate technique according to claim 4 prepares phosphoric acid coproduction land plaster, it is characterised in that: step c is returned
Return in the slurry weight in step a and step a, c be added phosphorus ore sulfuric acid weight and ratio be 30~50 ﹕ 1.
9. the method that hemihydrate technique according to claim 1 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step d
Mixed in obtained finished product phosphoric acid and cleaning solution return step c with sulfuric acid, back amount are as follows: guarantee step c in liquid-solid ratio be 5~
20 ﹕ 1.
10. the method that hemihydrate technique according to claim 2 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step d
Mixed in obtained finished product phosphoric acid and cleaning solution return step c with sulfuric acid, back amount are as follows: guarantee step c in liquid-solid ratio be 5~
20 ﹕ 1.
11. the method that hemihydrate technique according to claim 3 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step d
Mixed in obtained finished product phosphoric acid and cleaning solution return step c with sulfuric acid, back amount are as follows: guarantee step c in liquid-solid ratio be 5~
20 ﹕ 1.
12. the method that hemihydrate technique according to claim 4 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step d
Mixed in obtained finished product phosphoric acid and cleaning solution return step c with sulfuric acid, back amount are as follows: guarantee step c in liquid-solid ratio be 5~
20 ﹕ 1.
13. the method that hemihydrate technique according to claim 5 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step d
Mixed in obtained finished product phosphoric acid and cleaning solution return step c with sulfuric acid, back amount are as follows: guarantee step c in liquid-solid ratio be 5~
20 ﹕ 1.
14. the method that hemihydrate technique according to claim 6 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step d
Mixed in obtained finished product phosphoric acid and cleaning solution return step c with sulfuric acid, back amount are as follows: guarantee step c in liquid-solid ratio be 5~
20 ﹕ 1.
15. the method that hemihydrate technique according to claim 7 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step d
Mixed in obtained finished product phosphoric acid and cleaning solution return step c with sulfuric acid, back amount are as follows: guarantee step c in liquid-solid ratio be 5~
20 ﹕ 1.
16. the method that hemihydrate technique according to claim 8 prepares phosphoric acid coproduction land plaster, it is characterised in that: in step d
Mixed in obtained finished product phosphoric acid and cleaning solution return step c with sulfuric acid, back amount are as follows: guarantee step c in liquid-solid ratio be 5~
20 ﹕ 1.
17. according to the method that the described in any item hemihydrate techniques of claim 9~16 prepare phosphoric acid coproduction land plaster, feature exists
In: it is first uniformly mixed with the finished product phosphoric acid and cleaning solution returned in step d before sulfuric acid is added in step c.
18. the method that described in any item hemihydrate techniques prepare phosphoric acid coproduction land plaster, feature exist according to claim 1~16
In: each reaction time described in step a~c distinguishes > 2h, total reaction time > 6h.
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| BE1025894B1 (en) * | 2017-08-11 | 2020-02-21 | Prayon Tech | ACID ATTACK PROCESS OF A PHOSPHATE SOURCE |
| CN109628239A (en) * | 2018-12-17 | 2019-04-16 | 武汉飞博乐环保工程有限公司 | Produce method, ceramic cleaning agent and its production method of ceramic cleaning agent coproduction ultrawhite ardealite |
| CN110316708A (en) * | 2019-06-06 | 2019-10-11 | 贵州川恒化工股份有限公司 | The method that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum |
| CN110697669B (en) * | 2019-11-07 | 2023-07-11 | 中化重庆涪陵化工有限公司 | Method for improving wet-process phosphoric acid concentration and co-producing semi-hydrated gypsum |
| CN113185160B (en) * | 2021-04-21 | 2022-03-29 | 中国五环工程有限公司 | Method for controlling coarse large crystal of semi-hydrated gypsum |
| CN113173566B (en) * | 2021-04-21 | 2022-03-25 | 中国五环工程有限公司 | High-yield hydrated crystalline phase reconstruction wet-process phosphoric acid production process |
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| CN105253867A (en) * | 2015-09-18 | 2016-01-20 | 金正大生态工程集团股份有限公司 | Production method for by-product alpha-hemihydrate gypsum of wet-process phosphoric acid |
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| CN103086335A (en) * | 2013-02-05 | 2013-05-08 | 瓮福（集团）有限责任公司 | Method for production of phosphoric acid and combined production of a-hemihydrate gypsum through dehydrate-hemihydrate wet phosphoric acid technology |
| CN105253867A (en) * | 2015-09-18 | 2016-01-20 | 金正大生态工程集团股份有限公司 | Production method for by-product alpha-hemihydrate gypsum of wet-process phosphoric acid |
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